JP2018127546A - Composition for thermoplastic polymer film coating, manufacturing method of composition for thermoplastic polymer film coating, modified thermoplastic polymer film and manufacturing method of modified thermoplastic polymer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for thermoplastic polymer film coating exhibiting excellent flow drop from an initial term with expansion even when dry states and wet states are repeated, maintaining excellent flow drop over a long time even after expansion, further excellent in excoriation resistance, and extremely less in stickiness of a coated film surface, a manufacturing method of the composition, a modified thermoplastic polymer film using the composition and a manufacturing method of the modified thermoplastic polymer film.SOLUTION: As a composition for thermoplastic polymer film coating, one containing a specific (modified) inorganic cation colloid sol, polyether modified silicone, a specific polyoxyalkylene derivative and a specific ethylene oxide-propylene oxide block polymerization polymer at a specific ratio is used.SELECTED DRAWING: None

Description

  The present invention relates to a composition for coating a thermoplastic polymer film capable of imparting drip resistance having durability to a film used in an agricultural house, a method for producing such a composition, and heat of modification using such a composition. The present invention relates to a plastic polymer film and a method for producing such a modified thermoplastic polymer film.

  As a covering material for agricultural houses, thermoplastic polymer films are widely used. However, since the thermoplastic polymer film has a hydrophobic property, there is a problem that when cropping occurs and the transmission of sunlight is reduced, crops become poorly grown, and the attached water drops fall to cause disease. For this reason, conventionally, films used for agricultural houses have been proposed with nonionic surfactants added as anti-fogging agents and those containing colloidal silica and colloidal alumina as main components as droplets. In addition, an improvement in coating properties in the coating process, improvement in stickiness on the film surface, and drop in dropability due to friction during stretching have been proposed (see, for example, Patent Documents 1 to 4). However, these conventional thermoplastic polymer film coating compositions are insufficient to provide excellent drip properties that can withstand long-term use in agricultural house films that are repeatedly dried and wet. There is a problem.

JP-A-9-298554 JP 62-241984 JP 2000-160146 A Japanese Patent No. 5963923

  The problem to be solved by the present invention is that even when the dry state and the wet state are repeated, it exhibits excellent liquid dropability from the initial stage of stretching, and also exhibits excellent liquid dropability for a long time after the expansion. A composition for coating a thermoplastic polymer film that is excellent in scratch resistance and has a very low stickiness on the coated film surface, a method for producing such a composition, and a modified thermoplastic polymer using such a composition The present invention provides a film and a method for producing such a modified thermoplastic polymer film.

  As a result of researches to solve the above-mentioned problems, the present inventors contain a specific inorganic cation colloid sol, a polyether-modified silicone, a specific polyoxyalkylene derivative, and a specific ethylene oxide-propylene oxide block polymer in a specific ratio. It was found that the composition for coating a thermoplastic polymer film was correctly suitable.

  That is, in the present invention, the following inorganic cation colloid sol is 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass of the following polyoxyalkylene derivative, and a number average molecular weight of 1000 with respect to 100 parts by mass in terms of solid content. It relates to a thermoplastic polymer film coating composition comprising ˜9800 ethylene oxide-propylene oxide block polymer in a proportion of 45 to 75 parts by mass. Further, the present invention relates to the following modified inorganic cation colloid sol in terms of solid content of 100 parts by mass, 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass and the number average of the following polyoxyalkylene derivatives. A thermoplastic polymer film coating composition comprising an ethylene oxide-propylene oxide block polymer having a molecular weight of 1000 to 9800 in a proportion of 45 to 75 parts by mass. The present invention further relates to a method for producing such a composition, a modified thermoplastic polymer film using such a composition, and a method for producing such a modified thermoplastic polymer film.

  Inorganic cation colloid sol: Inorganic cation colloid comprising cation alumina sol in a proportion of 20 to 100% by mass in terms of solid content and cation silica sol in a proportion of 0 to 80% by mass in terms of solid content (total 100% by mass in terms of solid content) Sol.

  Modified inorganic cation colloid sol: Condensation polymer of the following silanol compound on solid content particles of the inorganic cation colloid sol: solid content of inorganic cation colloid sol / condensation polymer of silanol compound = 100/1 to 100/10 Modified inorganic cation colloid sol adhering at a ratio of (mass ratio).

  Silanol compound: A product obtained by hydrolyzing at least one silanol-forming organic silane compound selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes.

  Polyoxyalkylene derivative: a compound in which ethylene oxide is added in a ratio of 3 to 100 mol per 1 mol of the following starting compound, and random in a ratio of 3 to 100 mol in total of ethylene oxide and propylene oxide per 1 mol of the following starting compound And at least one compound selected from a compound in which ethylene oxide and propylene oxide are added in a block form at a ratio of 3 to 100 moles per mole of the following starting compound.

  Starting compound: at least one selected from an aliphatic alcohol having 8 to 22 carbon atoms, a fatty acid having 8 to 22 carbon atoms, an alkylphenol having 8 to 22 carbon atoms in an alkyl group, and a monoalkylamine having 8 to 22 carbon atoms.

  First, the thermoplastic polymer film coating composition according to the present invention (hereinafter referred to as the composition of the present invention) will be described. The composition of the present invention comprises 10 to 50 parts by mass of a polyether-modified silicone and 2 to 30 parts of a polyoxyalkylene derivative with respect to 100 parts by mass of the above-described inorganic cation colloid sol or modified inorganic cation colloid sol in terms of solid content. It contains 45 to 75 parts by mass of ethylene oxide-propylene oxide block polymerization polymer having a mass part and a number average molecular weight of 1000 to 9800, but the inorganic cation colloid sol or modified inorganic cation colloid sol is converted into solid content. More preferably, 20 to 40 parts by mass of the polyether-modified silicone, 5 to 20 parts by mass of the polyoxyalkylene derivative, and 50 to 70 parts by mass of the polyalkylene glycol with respect to 100 parts by mass.

  The inorganic cation colloid sol contains a cation alumina sol in a proportion of 20% or more, and optionally a cation silica sol can be used in combination. It is preferable to contain cationic alumina sol in a proportion of 20 to 100% by mass in terms of solids and cationic silica sol in a proportion of 0 to 80% by mass in terms of solids (total 100% by mass in terms of solids). What contains 30-100 mass% in conversion of minutes and cationic silica sol in the ratio of 0-70 mass% in conversion of solid content (a total of 100 mass% in conversion of solid content) is more preferable.

  Such cationic alumina sol is so-called colloidal alumina, and a commercially available aqueous dispersion can be used as it is. As such commercial products, for example, alumina sol 100, alumina sol 200, alumina sol 520 (all are trade names manufactured by Nissan Chemical Co., Ltd.), cataloid AS-1, cataloid AS-2, cataloid AS-3J (all are JGC) For example, a product name manufactured by Catalyst Kasei Co., Ltd.).

  As such a cationic silica sol, a commercially available aqueous dispersion can be used as it is. Examples of such commercially available products include SNOWTEX AK, SNOWTEX AK-L (all are trade names manufactured by Nissan Chemical Co., Ltd.), Cataloid SN (trade names manufactured by JGC Catalysts & Chemicals Co., Ltd.), Quattron PL-3- C (trade name manufactured by Fuso Chemical Industry Co., Ltd.) and the like.

  The particle diameter of the inorganic cation sol is represented by an average particle diameter or a secondary dispersion diameter, and an average particle diameter of 5 to 50 nm and a secondary dispersion diameter of 50 to 200 nm can be used. Examples of the method for measuring the particle diameter include observation with a transmission electron microscope and specific surface area measurement using a BET adsorption method.

  In the composition of the present invention, it is preferable to use a modified inorganic cation colloid sol instead of the inorganic cation colloid sol described above. The modified inorganic cation colloid sol is obtained by hydrolyzing a silanol-forming organic silane compound, and then condensing and polymerizing the produced silanol compound to adhere to the inorganic cation colloid sol.

  The silanol compound condensation polymer adhering to the surface of the solid particles (alumina or silica colloid particles) of the modified inorganic cation colloid sol hydrolyzes the silanol-forming organosilane compound, It can be obtained by condensation polymerization. As will be described in detail later, the silanol-forming organic silane compound is hydrolyzed in the presence of the inorganic cation colloid sol, and the resulting silanol compound is subsequently subjected to condensation polymerization to form solid particles of the inorganic cation colloid sol. A modified inorganic cation colloidal sol having a silanol compound condensation polymer adhered thereto can be obtained.

  Examples of such silanol-forming organosilane compounds include 1) methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ-chloropropyltripropoxysilane, γ-mercaptopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, trialkoxysilanes such as phenyltrimethoxysilane, 2) dimethyldimethoxysilane, γ-chloropropylmethyldimethoxy Dialkoxysilanes such as silane and γ-glycidoxypropylmethyldimethoxysilane, and 3) monoalkoxysilanes such as trimethylchlorosilane and trimethylmethoxysilane.Of these, γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, methyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable.

  In such a modified inorganic cation colloid sol, a condensation polymer of a silanol compound is attached in such a form that all or part of the surface of the solid particles of the inorganic cation colloid sol is coated, and a part of the inorganic cation colloid sol is inorganic cation. It is presumed that they are chemically bonded to the solid particles of the colloidal sol. In such a modified inorganic cation colloid sol, the condensation polymer of the silanol compound is added to the solid content particle of the inorganic cation colloid sol, and the solid content of the inorganic cation colloid sol / condensation polymer of the silanol compound = 100/1 to 100/10 (mass). Ratio) is preferred, but the solid content of inorganic cationic colloidosol / condensation polymer of silanol compound = 100/2 to 100/8 (mass ratio). More preferred.

  As the polyether-modified silicone to be used for the composition of the present invention, commercially available products can be used as they are. Examples of such commercially available products include TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, and TSF4460 (all of which are trade names of Momentive Performance Materials Japan), X22-4952, X-22-4272, and KF. -6123, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6204 X-22-4515, KF-6004 (all are trade names manufactured by Shin-Etsu Silicone), SH8700, SH8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203, FZ-2208 (all the above Dow Corning Toray Co., Ltd. under the trade name), but and the like, and among them, TSF4440, KF-354L, KF-945, SH8400, KF-6004, etc., HLB is preferably from 4 to 16.

  The polyoxyalkylene derivative provided for the composition of the present invention is a compound in which ethylene oxide is added to the following starting materials and a compound in which ethylene oxide and propylene oxide are used in combination, and ethylene oxide and propylene oxide are used in combination. When added, it may have either a block or random structure. The number of moles added is 3 to 100 moles in total when ethylene oxide and propylene oxide are added together when ethylene oxide alone is added to 1 mole of the following starting material. Is preferable, and 5-50 mol is more preferable.

  Starting compound: at least one selected from an aliphatic alcohol having 8 to 22 carbon atoms, a fatty acid having 8 to 22 carbon atoms, an alkylphenol having 8 to 22 carbon atoms in an alkyl group, and a monoalkylamine having 8 to 22 carbon atoms

  The starting compound to be used in the composition of the present invention is an aliphatic alcohol having 8 to 22 carbon atoms, a fatty acid having 8 to 22 carbon atoms, an alkylphenol having 8 to 22 carbon atoms in an alkyl group, or an alkyl group having 8 to 22 carbon atoms. And an aliphatic alcohol having 8 to 22 carbon atoms, such as capryl alcohol, 2-ethylhexyl alcohol, pelargon alcohol, caprin alcohol, undecyl alcohol, 2 having 9 to 11 carbon atoms. Grade alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, lysylyl alcohol, behenyl alcohol, etc., and fats having 8 to 22 carbon atoms Examples include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, eicosanoic acid, behenic acid, etc., and the alkyl group has 8 to 8 carbon atoms. Examples of the 22 alkylphenol include octylphenol, nonylphenol, decylphenol, dodecylphenol, octadecylphenol and the like, and monoalkylamines having 8 to 22 carbon atoms in the alkyl group include caprylamine, nonylamine, decylamine, laurylamine, trilamine. Examples include decylamine, myristylamine, stearylamine, oleylamine, and behenylamine. Among them, aliphatic alcohols having 8 to 22 carbon atoms and fatty acids having 8 to 22 carbon atoms are more preferable.

  The polyoxyalkylene derivative to be used for the composition of the present invention is as described above. Specifically, as the ethylene oxide adduct of an aliphatic alcohol having 8 to 22 carbon atoms, a capryl alcohol ethylene oxide 5 mol adduct is used. , 2-ethylhexyl alcohol ethylene oxide 100 mol adduct, pelargon alcohol ethylene oxide 5 mol adduct, undecyl alcohol ethylene oxide 30 mol adduct, secondary alcohol ethylene oxide 9 mol adduct having 9 to 11 carbon atoms, lauryl alcohol ethylene oxide 10 mol adduct , Palmityl alcohol ethylene oxide 50 mol adduct, stearyl alcohol ethylene oxide 20 mol adduct, isostearyl alcohol ethylene oxide 20 mol adduct, oleyl alcohol Examples include 14 mole adducts of lenoxide, 24 moles of behenyl alcohol ethylene oxide, and the like, and adducts using ethylene oxide and propylene oxide of aliphatic alcohols having 8 to 22 carbon atoms include capryl alcohol ethylene oxide 10 mol propylene oxide 10 mol random Adduct, 2-ethylhexyl alcohol propylene oxide 30 mol ethylene oxide 30 mol adduct, caprin alcohol ethylene oxide 30 mol propylene oxide 20 mol random adduct, lauryl alcohol ethylene oxide 9 mol propylene oxide 9 mol random adduct, tridecyl alcohol ethylene oxide 10 mol propylene Oxide 10 mole random adduct, ethylene oxide 1 of aliphatic mixed alcohol having 12 to 13 carbon atoms Mole propylene oxide 10 mol random adduct, myristyl alcohol propylene oxide 13 mol ethylene oxide 10 mol block adduct, tetradecyl alcohol propylene oxide 13 mol ethylene oxide 11 mol block adduct, pentadecyl alcohol propylene oxide 13 mol ethylene oxide 10 mol block adduct, Examples thereof include propylene oxide 13 mol ethylene oxide 11 mol block adducts of aliphatic mixed alcohols having 14 to 15 carbon atoms, and ethylene oxide adducts of fatty acids having 8 to 22 carbon atoms include 10 mol adducts of caprylic acid ethylene oxide and lauric acid. Ethylene oxide 12 mol adduct, palmitic acid ethylene oxide 5 mol adduct, stearic acid ethylene oxide 13 mol adduct, oleic acid ethyl Examples include 13-mole adducts of lenoxide, and examples of adducts using ethylene oxide and propylene oxide of fatty acids having 8 to 22 carbon atoms include ethylene oxide caprylate 10 mol propylene oxide 10 mol random adduct, capric acid ethylene oxide 40 mol propylene. Oxide 10 mol random adduct, Lauric acid ethylene oxide 10 mol Propylene oxide 10 mol random adduct, Myristate propylene oxide 13 mol Ethylene oxide 10 mol block adduct, Pentadecanoic acid propylene oxide 13 mol ethylene oxide 10 mol block adduct, Oleic acid propylene oxide 24 mol ethylene oxide 24 mol block adduct, behenate ethylene oxide 10 propylene oxide 10 mol random adduct, etc. Examples of the ethylene oxide adducts of alkylphenols having 8 to 22 carbon atoms in the alkyl group include octylphenol ethylene oxide 3 mol adduct, nonylphenol ethylene oxide 10 mol adduct, decylphenol ethylene oxide 12 mol adduct, dodecylphenol ethylene oxide 100 mol adduct, and the like. Examples of the adducts in which ethylene oxide and propylene oxide of an alkylphenol having 8 to 22 carbon atoms in the alkyl group are used in combination include octylphenol ethylene oxide 50 mol propylene oxide 10 mol random adduct, nonylphenol propylene oxide 10 mol ethylene oxide 35 mol random adduct Decylphenol propylene oxide 3 mol ethylene oxide 10 mol block block adduct, octa Examples thereof include silphenol propylene oxide 10 mol ethylene oxide 80 mol random adduct, and the like. Examples of the ethylene oxide adduct of monoalkylamine having 8 to 22 carbon atoms in the alkyl group include caprylamine ethylene oxide 4 mol adduct, laurylamine ethylene oxide 10 mol. Examples include adducts, myristylamine ethylene oxide 20 mol adduct, stearylamine ethylene oxide 45 mol adduct, and the like. As an adduct using a monoalkylamine ethylene oxide having 8 to 22 carbon atoms and propylene oxide in combination, capryl Amine ethylene oxide 20 mol propylene oxide 10 mol random adduct, laurylamine ethylene oxide 10 mol propylene oxide 10 mol random adduct, palmitylamine propylene Examples include a 10-mol ethylene oxide 20-mol block adduct, a stearylamine propylene oxide 20-mol ethylene oxide 60-mol block adduct, and a behenylamine ethylene oxide 20-mol propylene oxide 5-mol block adduct. Among them, ethylene oxide adducts of aliphatic alcohols having 8 to 22 carbon atoms, adducts using ethylene oxide and propylene oxide of aliphatic alcohols having 8 to 22 carbon atoms, ethylene oxide adducts of fatty acids having 8 to 22 carbon atoms, and carbon An adduct of ethylene oxide and propylene oxide in combination with several 8 to 22 fatty acids, and 5 to 50 mol of ethylene oxide and 5 to 50 mol in total of ethylene oxide and propylene oxide with respect to 1 mol of starting material Preferred are those having 12 to 13 aliphatic mixed alcohol ethylene oxide 10 moles propylene oxide 10 mole random adduct, lauryl alcohol ethylene oxide 10 mole adduct, aliphatic mixed secondary alcohol ethylene oxide having 9 to 11 carbon atoms. With 9 moles Oleyl alcohol ethylene oxide 14 mol adduct, stearyl alcohol ethylene oxide 20 mol adduct, C14-15 aliphatic mixed alcohol propylene oxide 13 mol ethylene oxide 11 mol block adduct, caprylic acid ethylene oxide 10 mol adduct, lauric acid ethylene oxide 12 mol adduct, stearic acid ethylene oxide 13 mol adduct, behenyl alcohol ethylene oxide 24 mol adduct, lauryl alcohol ethylene oxide 9 mol propylene oxide 9 mol random adduct, oleic acid propylene oxide 24 mol ethylene oxide 24 mol adduct, oleic acid ethylene oxide 13 mol Examples include adducts, lauryl alcohol ethylene oxide 5 mol adducts, and the like.

  The ethylene oxide-propylene oxide block polymer to be used in the composition of the present invention has a number average molecular weight of 1000 to 9800, preferably a number average molecular weight of 2000 to 6000. Moreover, the thing whose polymerization ratio of ethylene oxide is 5-50 mass% is preferable, and the thing of 15-45 mass% is still more preferable. The coupling mode of ethylene oxide and propylene oxide is as follows: block of units formed from ethylene oxide-block of units formed from propylene oxide, block of units formed from propylene oxide-block of units formed from ethylene oxide, from ethylene oxide Block of units formed-Block of units formed from propylene oxide-Block of units formed from ethylene oxide (hereinafter referred to as E-PE type), Block of units formed from propylene oxide-Formed from ethylene oxide Examples of such a unit block include a unit block formed from propylene oxide (hereinafter referred to as P-E-P type), and the E-P-E type is preferred. The number average molecular weight can be calculated from the hydroxyl value, and the hydroxyl value can be determined by the method described in JIS K0070.

  Next, the manufacturing method of the composition for thermoplastic polymer film coating according to the present invention (hereinafter referred to as the manufacturing method of the composition of the present invention) will be described. The manufacturing method of the composition of this invention is a manufacturing method which passes through the following 1st process and 2nd process.

First step: Hydrolyzing a silanol-forming organosilane compound in the presence of the following inorganic cation colloid sol, and further subjecting the produced silanol compound to condensation polymerization, 1 per 100 parts by mass of the solid content of the inorganic cation colloid sol Step of obtaining a modified inorganic cation colloid sol by adhering in an amount of 10 to 10 parts by mass Inorganic cation colloid sol: 20 to 100% by mass of cation alumina sol in terms of solid content and 0 to 80 in terms of solid content of cation silica sol Inorganic cation colloidal sol containing in a proportion of mass% (total 100 mass% in terms of solid content)

  Second step: The modified inorganic cation colloid sol obtained in step 1 is 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass and a number average of polyoxyalkylene derivatives with respect to 100 parts by mass in terms of solid content. A step of blending an ethylene oxide-propylene oxide block polymer having a molecular weight of 1000 to 9800 in a proportion of 45 to 75 parts by mass to obtain a composition for coating a thermoplastic polymer film

  In the method for producing the composition of the present invention, the inorganic cation colloid sol and the silanol-forming organosilane compound used in the first step are the same as described above, including the ratio of the condensation polymer of the inorganic cation colloid sol and the silanol compound. In addition, the polyether-modified silicone, polyoxyalkylene derivative and polyalkylene glycol used in the second step are as described above, including their proportions.

Next, the modified thermoplastic polymer film according to the present invention (hereinafter referred to as the film of the present invention) will be described. The film of the present invention is such that the above-described composition of the present invention adheres in an amount of 0.1 to 2.0 g / m ² as a solid content on the surface-treated surface of a thermoplastic polymer film.

  The film of the present invention is obtained by surface-treating the surface of a thermoplastic polymer film to which the composition of the present invention is applied, and then applying the composition of the present invention. Examples of the surface treatment include known methods such as corona discharge treatment, atmospheric pressure plasma treatment, and flame treatment, but corona discharge treatment is preferred. The wetting tension of the surface treated surface is preferably 35 mN / m or more, and more preferably 35 to 70 mN / m. In the present invention, the wetting tension is a value measured according to the description of JIS-K6768.

Examples of the thermoplastic resin used in the film of the present invention include 1) polyolefin resin, 2) polyvinyl chloride resin, and 3) polyester resin. Examples of polyolefin resins include homopolymers of α-olefins such as polyethylene and polypropylene, ethylene-propylene copolymers, ethylene / 1-butene copolymers, ethylene / 4-methyl-1-pentene copolymers, ethylene Α-olefin copolymer such as 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate / methyl methacrylate copolymer Copolymers and copolymers with different monomers based on α-olefins such as ionomer resins are listed. Examples of polyvinyl chloride resins include polyvinyl chloride, vinyl chloride / ethylene copolymers, vinyl chloride / acetic acid. Examples include vinyl copolymers, vinyl chloride / methyl methacrylate copolymers, and polyvinylidene chloride. Polyester as the resin of polyethylene terephthalate, polyethylene terephthalate naphthalate and the like, may be used by blending plural types of resins. Of these, polyolefin resins are preferred. The α-olefin copolymer in the polyolefin resin is more preferably one obtained by a gas phase method, a solution polymerization method or the like using a homogeneous catalyst such as a known highly active Ziegler catalyst or a metallocene catalyst, and has a density. Particularly preferred is 0.86 to 0.94 g / cm ³ and an MFR of 0.01 to 20 g / 10 min. The polyolefin resin can be used by mixing two or more polyolefin resins. These thermoplastic resins contain commonly used antioxidants, weathering agents, ultraviolet absorbers, infrared absorbers, lubricants, antiblocking agents, antifogging agents, antifogging agents, heat retention agents, pigments, etc. as necessary. Can be contained.

  There is no restriction | limiting in particular as a manufacturing method of the thermoplastic polymer film with which it uses for the film of this invention, For example, the inflation molding method, T-die molding method, etc. are mentioned. The film may be a single layer film or a multilayer film, and may be an unstretched film or a stretched film. As the agricultural film, a thermoplastic polymer film made of the polyolefin resin formed by inflation molding is suitable.

  Although there is no restriction | limiting in particular in the use of the film of this invention, When using for the coating film for agriculture, expression of an effect is remarkable.

  Finally, a method for producing the modified thermoplastic polymer film according to the present invention (hereinafter referred to as the film production method of the present invention) will be described. The manufacturing method of the film of this invention is a manufacturing method which passes through the following 1st process and the following 2nd process.

  1st process: The process which surface-treats to a thermoplastic polymer film, and sets the wet tension of a process surface to 35 mN / m or more

2nd process: The process of apply | coating the above-mentioned composition of this invention so that it may become 0.1-2.0 g / m < ² > as solid content with respect to the surface treatment surface of the thermoplastic polymer film obtained at the 1st process.

  In the film production method of the present invention, the thermoplastic polymer film is as described above. The first step is a step of subjecting the thermoplastic polymer film to surface treatment so that the wet tension of the treated surface is 35 mN / m or more, but it is effective to make the wet tension within the range of 35 to 70 mN / m. Is easy to express and is preferable. The surface treatment can be performed by a known method such as corona discharge treatment, atmospheric pressure plasma treatment, flame treatment, etc., but corona discharge treatment is preferred. In the present invention, the wetting tension is a value measured according to the description of JIS-K6768.

Moreover, a 2nd process apply | coats the above-mentioned composition of this invention to 0.1-2.0 g / m < ² > as solid content with respect to the surface treatment surface of the thermoplastic polymer film obtained at the 1st process. It is a process. In order to apply the composition of the present invention to the thermoplastic polymer film, a known coating method can be used. Examples thereof include a spray coating method, a dip coating method, a roll coating method, a doctor blade coating method, a wire bar coating method, and an air knife coating method.

  According to the present invention described above, even when it is used while being repeatedly dried and wet, it exhibits excellent drip properties from the initial stage of stretching, and maintains excellent drip properties for a long time after spreading. It has excellent scratch resistance, and has an effect that the coated film surface is extremely less sticky.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test Category 1 (Preparation of a composition for coating a thermoplastic polymer film)
Example 1
An inorganic cationic colloidal sol was prepared by mixing 331.3 parts of water and 740.7 parts of cationic alumina sol (X1-1) (solid content: 13.5%). This inorganic cation colloid sol is mixed with 8 parts of a silanol-forming organosilane compound (Y-1) to prepare a mixed solution having a solid content of 10%, and stirred at 50 ° C. for 5 hours to obtain a silanol-forming organosilane compound ( Y-1) was hydrolyzed, and the produced silanol compound was subjected to condensation polymerization to obtain a modified inorganic cation colloid sol (A-1). In this modified inorganic cation colloid sol (A-1), a condensation polymerization product of a silanol compound was adhered to the solid particles of the inorganic cation colloid sol. Next, 100 parts of this modified inorganic cation colloid sol (A-1) in terms of solid content, 8900 parts of water, 30 parts of polyether-modified silicone (B-1), 10 parts of polyoxyalkylene derivative (C-1) And 60 parts of ethylene oxide-propylene oxide block polymer (D-1) was added and stirred to obtain a composition (S-1) for coating a thermoplastic polymer film having a solid content concentration of 2%.

-Examples 2-37 and Comparative Examples 1-19
In the same manner as in Example 1, (modified) inorganic cation colloid sols (A-2) to (A-13) and (ar-1) to (ar-3) were prepared. 37 and compositions (S-2) to (S-37) and (sr-1) to (sr-19) for thermoplastic polymer film coating of Comparative Examples 1 to 19 were obtained. The contents of the (modified) inorganic cation colloid sol prepared in each of the above examples are summarized in Table 1, and the contents of the thermoplastic polymer film coating composition obtained in each of the above examples are shown in Tables 2 and 3. Are summarized in

In Table 1,
X1-1: Feather crystal type alumina sol having a particle diameter of 7 to 15 nm X1-2: Fibrous crystal type alumina sol having a secondary dispersion diameter of 100 to 150 nm X1-3: Plate-like crystal type alumina sol having a particle diameter of 15 to 30 nm X2-1 : Alumina-modified silica sol having a particle diameter of 10 to 15 nm X2-2: Alumina-modified silica sol having a particle diameter of 10 to 14 nm X2-3: Alumina-modified silica sol having a particle diameter of 30 to 40 nm Y-1: γ-glycidoxypropyltrimethoxysilane Y -2: γ-ureidopropyltrimethoxysilane Y-3: methyltriethoxysilane Y-4: γ-methacryloxypropyltrimethoxysilane Y-5: γ-glycidoxypropylmethyldimethoxysilane Y-6: trimethylmethoxysilane

In Table 2 and Table 3,
A-1 to A-13, ar-1 to ar-3: (modified) inorganic cation colloidal sol described in Table 1 B-1: polyether-modified silicone (product of Momentive Performance Materials Japan) Name TSF4440, HLB = 14)
B-2: Polyether-modified silicone (trade names KF-354L, HLB = 16 manufactured by Shin-Etsu Silicone)
B-3: Polyether-modified silicone (trade name KF-945 manufactured by Shin-Etsu Silicone, HLB = 4)
B-4: Polyether-modified silicone (trade names SH8400, HLB = 8 manufactured by Toray Dow Corning)
B-5: Polyether-modified silicone (trade name KF-6004 manufactured by Shin-Etsu Silicone, HLB = 9)
BR-1: Polydimethyl silicone (trade name KF-96 manufactured by Shin-Etsu Silicone)
BR-2: Long chain alkyl-modified silicone (trade name KF-412 manufactured by Shin-Etsu Silicone)

C-1: Ethylene oxide 10 mol propylene oxide 10 mol random adduct of C12-13 aliphatic mixed alcohol C-2: Ethylene oxide 10 mol adduct of lauryl alcohol C-3: Aliphatic mixture of C9-11 Ethylene oxide 9 mol adduct of secondary alcohol C-4: Ethylene oxide 14 mol adduct of oleyl alcohol C-5: Ethylene oxide 20 mol adduct of stearyl alcohol C-6: Propylene oxide of aliphatic mixed alcohol having 14 to 15 carbon atoms 13 mol ethylene oxide 11 mol block adduct C-7: ethylene oxide 10 mol adduct of caprylic acid C-8: ethylene oxide 12 mol adduct of lauric acid C-9: ethylene oxide 13 mol adduct of stearic acid C-10: behenyl alcohol Tylene oxide 24 mol adduct C-11: 9 mol of ethylene oxide of lauryl alcohol 9 mol random adduct of propylene oxide C-12: 24 mol of propylene oxide of oleic acid 24 mol block adduct C-13: 13 mol of ethylene oxide of oleic acid Adduct C-14: Lauryl alcohol ethylene oxide 5 mol adduct C-15: Caprylamine ethylene oxide 4 mol adduct C-16: Nonylphenol ethylene oxide 10 mol adduct C-17: 2-ethylhexyl alcohol ethylene oxide 100 mol adduct CR-1 : Methanol CR-2: Ethylene glycol

D-1: Ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization rate 20%, number average molecular weight 2200)
D-2: Ethylene oxide-propylene oxide block polymerization polymer (E-P-E type, ethylene oxide polymerization ratio 30%, number average molecular weight 5000)
D-3: Ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization rate 17%, number average molecular weight 5000)
D-4: Ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization ratio 34%, number average molecular weight 2900)
D-5: Ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization ratio 15%, number average molecular weight 6000)
D-6: Ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization ratio 45%, number average molecular weight 2000)
D-7: Ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization ratio 5%, number average molecular weight 1000)
D-8: ethylene oxide-propylene oxide block polymerization polymer (EPE type, ethylene oxide polymerization ratio 50%, number average molecular weight 9500)
DR-1: Polyethylene glycol (trade name PEG-400 manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 400)
DR-2: Polyethylene glycol (trade name Alcox R-150 manufactured by Meisei Chemical Industry Co., Ltd., number average molecular weight 150,000)
DR-3: Polyethylene glycol (trade name PEG-10000, number average molecular weight 11000, manufactured by Sanyo Chemical Industries)
DR-4: Random polymerized ethylene oxide-propylene oxide (ethylene oxide polymerization ratio 50%, number average molecular weight 3500)
DR-5: ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization rate 25%, number average molecular weight 700)
DR-6: ethylene oxide-propylene oxide block polymer (EPE type, ethylene oxide polymerization rate 83%, number average molecular weight 14600)

Test Category 2 (Manufacture of modified thermoplastic polymer film)
Example 38
An ethylene / 1-butene copolymer (ethylene copolymer ratio 96%, density 0.930 g / cm ³ , MFR 1.0 g / 10 min) was subjected to an inflation molding machine equipped with a die having a diameter of 75 mm and a lip gap of 3 mm, Inflation molding was carried out under the conditions of a resin extrusion temperature of 200 ° C. and BUR = 1.8 to produce an olefin polymer film having a thickness of 150 μm. Next, the olefin polymer film is subjected to corona treatment discharge, the wet tension of the corona discharge treatment surface is set to 44 mN / m, and then the thermoplastic polymer film coating composition prepared in Test Category 1 on the corona discharge treatment surface. (S-1) was applied by a gravure coating method so as to be 0.3 g / m ² as a solid content, and was allowed to stay in a warm air drying furnace adjusted to 70 ° C. for 1 minute. A molecular film was obtained.

Examples 39 to 74 and comparative examples 20 to 38
In the same manner as in Example 38, modified thermoplastic polymer films of Examples 39 to 74 and Comparative Examples 20 to 38 were obtained. Tables 4 and 5 collectively show the contents of the modified thermoplastic polymer films produced in the above examples.

Test category 3 (evaluation of modified thermoplastic polymer film)
・ Evaluation of initial dropability and long-term dropability The 15 degree inclination of the modified thermoplastic polymer film of each example manufactured in Test Category 2 was adjusted to an internal temperature of the house of 30 ° C and an external temperature of the house of 10 ° C. A test house having a surface was covered with 1 m ² , and the state of water droplet adhesion was observed in the initial stage (after 1 day) and in the long term (after 30 days), and the water droplet prevention effect, that is, the droplet property was evaluated according to the following criteria. The results are summarized in Table 4 and Table 5.

Evaluation criteria of flowability 5: No water droplet adhesion 4: Water droplet adhesion area less than 10% 3: Water droplet adhesion area of 10% to less than 50% 2: Water droplet adhesion area of 50% to less than 80% 1: Water drop adhesion area is 80% or more

・ Evaluation of Repeated Droplet Properties 15 degree under the condition that the modified thermoplastic polymer film of each example produced in Test Category 2 was adjusted to a water temperature of 10 ° C. and an external temperature of 30 ° C. above the water tank. Then, it was stretched for 24 hours to be in a wet state, then removed and dried for 24 hours, and then stretched again on the top of the water tank in the same manner as described above. The state of water droplet adhesion after repeating this 10 times was confirmed, and the droplet property was evaluated according to the same criteria as the initial droplet property and the long-term droplet property.

・ Evaluation of scratch resistance Each of the products manufactured in Test Category 2 by applying a 300 g load on the friction surface of the arm of a friction tester (Gakushin dyeing fastness tester manufactured by Daiei Kagaku Seisakusho Co., Ltd.) and applying a load of 300 g. After 10 reciprocating rubs on the coated surface 100 cm ² of the modified thermoplastic polymer film of the example, steam is applied to the rubbed part, and the degree of peeling of the coating film is observed by the cloudy part formed by water droplets attached, The peel resistance, that is, scratch resistance, of the coating film was evaluated according to the following criteria. The results are summarized in Table 4 and Table 5.

Evaluation criteria of scratch resistance 5: No peeling of the coating film 4: The peeling area of the coating film is less than 10% 3: The peeling area of the coating film is 10% to less than 50% 2: The peeling area of the coating film is 50% or more ˜less than 80% 1: peeling area of coating film is 80% or more

・ Evaluation of stickiness Two 20 cm × 20 cm square sample pieces were cut out from the modified thermoplastic polymer film of each example produced in Test Category 2, the application surfaces of the sample pieces were overlapped, and a load of 1 kg / m ² was applied. Evenly held at 50 ° C. for 24 hours, the stacked film is cut into 10 mm × 10 mm squares to form test pieces, and the peel strength between the two films, that is, the stickiness of the test pieces, based on the following criteria: evaluated. The results are summarized in Table 4 and Table 5.

Stickiness Evaluation Criteria 5: Peeling force is less than 50 mN / 10 mm 4: Peeling force is 50 mN / 10 mm or more to less than 100 mN / 10 mm 3: Peeling force is 100 mN / 10 mm or more to less than 150 cmN / 10 mm 2: Peeling force is 150 mN / 10 mm or more to less than Less than 200 mN / 10 mm 1: Peeling force is 200 mN / 10 mm or more

-Evaluation of liquid stability The state of separation when the thermoplastic polymer film coating composition of each example prepared in Test Category 1 was stored at room temperature 20 ° C in a sealed container was observed and separated. The liquid stability was evaluated according to the following criteria depending on the time until the completion The results are summarized in Table 4 and Table 5.

Evaluation criteria of liquid stability 5: No separation for 24 hours or more 4: No separation for 12 hours or more to less than 24 hours 3: No separation for 6 hours or more to less than 12 hours 2: No separation for 2 hours or more to less than 6 hours 1: 2 hours Less than

-Evaluation of applicability The state of the application surface of the modified thermoplastic polymer film of each example produced in Test Category 2 was observed, and applicability was evaluated according to the following criteria. The results are summarized in Table 4 and Table 5.

Evaluation criteria for applicability 5: No unevenness or repellency occurred 4: Partial unevenness occurred 3: Unevenness occurred throughout the entire surface 2: Partial repellent occurred 1: Entire Repelling has occurred

  As is apparent from the results of Tables 4 and 5 corresponding to Tables 1 to 3, when the composition of the present invention was applied, it was excellent from the initial stage of spreading even when it was used while being dried and wet. It can be seen that it exhibits fluidity, maintains excellent fluidity over a long period of time after stretching, and also has excellent scratch resistance, and the coated film surface has very little stickiness.

Claims (13)

The following inorganic cationic colloidal sol is 100 parts by mass in terms of solid content, 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass of the following polyoxyalkylene derivative, and ethylene oxide having a number average molecular weight of 1000 to 9800. A composition for coating a thermoplastic polymer film, comprising a propylene oxide block polymer at a ratio of 45 to 75 parts by mass.
Inorganic cation colloid sol: Inorganic cation colloid comprising cation alumina sol in a proportion of 20 to 100% by mass in terms of solid content and cation silica sol in a proportion of 0 to 80% by mass in terms of solid content (total 100% by mass in terms of solid content) Sol Polyoxyalkylene derivative: Compound in which ethylene oxide is added in a ratio of 3 to 100 mol per 1 mol of the following starting compound, and random in a ratio of 3 to 100 mol in total of ethylene oxide and propylene oxide per 1 mol of the following starting compound At least one selected from the compound added in the form of a block and the compound in which ethylene oxide and propylene oxide are added in a block form in a proportion of 3 to 100 moles per mole of the following starting compound: Starting compound: 8 to 8 carbon atoms 22 fatty alcohols, fats with 8-22 carbon atoms , At least one selected from alkylphenols and monoalkyl amines having 8 to 22 carbon atoms of 8-22 carbon atoms in the alkyl group The following modified inorganic cation colloid sol is 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass of the following polyoxyalkylene derivative, and a number average molecular weight of 1000 to 9800 with respect to 100 parts by mass in terms of solid content. A thermoplastic polymer film coating composition comprising an ethylene oxide-propylene oxide block polymerization polymer in a proportion of 45 to 75 parts by mass.
Modified inorganic cation colloid sol: Condensation polymer of the following silanol compound on solid content particles of the following inorganic cation colloid sol: solid content of inorganic cation colloid sol / condensation polymer of silanol compound = 100/1 to 100/10 Modified inorganic cation colloid sol adhering at a ratio of (mass ratio).
Inorganic cation colloid sol: Inorganic cation colloid comprising cation alumina sol in a proportion of 20 to 100% by mass in terms of solid content and cation silica sol in a proportion of 0 to 80% by mass in terms of solid content (total 100% by mass in terms of solid content) Sol Silanol compound: Hydrolyzed at least one silanol-forming organic silane compound selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes.
Polyoxyalkylene derivative: a compound in which ethylene oxide is added in a ratio of 3 to 100 mol per 1 mol of the following starting compound, and random in a ratio of 3 to 100 mol in total of ethylene oxide and propylene oxide per 1 mol of the following starting compound And at least one compound selected from a compound in which ethylene oxide and propylene oxide are added in a block form in a proportion of 3 to 100 moles per mole of the following starting compound and starting compound: 8 to 22 carbon atoms At least one selected from aliphatic alcohols of the above, fatty acids having 8 to 22 carbon atoms, alkylphenols having 8 to 22 carbon atoms in the alkyl group, and monoalkylamines having 8 to 22 carbon atoms   The composition for thermoplastic polymer film coating according to claim 1 or 2, wherein the ethylene oxide-propylene oxide block polymerization polymer has a number average molecular weight of 2000 to 6000.   The composition for thermoplastic polymer film coating according to any one of claims 1 to 3, wherein the ethylene oxide-propylene oxide block polymerization polymer has a polymerization ratio of ethylene oxide of 5 to 50% by mass.   The composition for thermoplastic polymer film coating according to any one of claims 1 to 3, wherein the ethylene oxide-propylene oxide block polymerization polymer has a polymerization ratio of ethylene oxide of 15 to 45 mass%.   The composition for coating a thermoplastic polymer film according to any one of claims 1 to 5, wherein the polyether-modified silicone has an HLB of 4 to 16. Polyoxyalkylene derivative is a compound in which ethylene oxide is added at a rate of 5 to 50 mol per 1 mol of the following starting compound, and ethylene oxide and propylene oxide are randomly added at a rate of 5 to 50 mol per mol of the following starting compound. 7. The compound added in the form of a block and at least one selected from the compounds wherein ethylene oxide and propylene oxide are added in a block form in a ratio of 5 to 50 moles in total per mole of the following starting compound: The composition for thermoplastic polymer film coating according to any one of the above.
Starting compound: at least one selected from aliphatic alcohols having 8 to 22 carbon atoms and fatty acids having 8 to 22 carbon atoms The manufacturing method of the composition for thermoplastic polymer film coating characterized by passing through the following 1st process and the following 2nd process.
First step: In the presence of the following inorganic cation colloid sol, a silanol-forming organosilane compound in an amount of 1 to 10 parts by mass per 100 parts by mass of the solid content of the inorganic cation colloid sol is hydrolyzed, Further, a step of obtaining a modified inorganic cation colloid sol by condensation polymerization of the produced silanol compound Inorganic cation colloid sol: 20-100% by mass in terms of solid content of cation alumina sol and 0-80% by mass in terms of solid content of cation silica sol ( Inorganic cation colloid sol comprising a proportion of 100% by mass in terms of solid content) Second step: Polyether-modified silicone with respect to 100 parts by mass of the modified inorganic cation colloid sol obtained in step 1 in terms of solid content 10 to 50 parts by mass, 2 to 30 parts by mass of the following polyoxyalkylene derivative and number average molecular weight A step of blending 000-9800 ethylene oxide-propylene oxide block polymer at a ratio of 45-75 parts by mass to obtain a composition for coating a thermoplastic polymer film Polyoxyalkylene derivative: 3 ethylene oxides per mol of the following starting compound A compound added at a ratio of ˜100 mol, a compound wherein ethylene oxide and propylene oxide are added randomly at a ratio of 3 to 100 mol per mol of the following starting compound, and ethylene oxide per mol of the following starting compound And at least one compound selected from compounds in which propylene oxide is added in a block form in a proportion of 3 to 100 mol Starting compound: aliphatic alcohol having 8 to 22 carbon atoms, fatty acid having 8 to 22 carbon atoms, alkyl group Of 8 to 22 carbon atoms At least one selected from the group consisting Lumpur and monoalkyl amines having 8 to 22 carbon atoms The thermoplastic polymer film coating composition according to any one of claims 1 to 7 is adhered to the surface-treated surface of the thermoplastic polymer film in an amount of 0.1 to 2.0 g / m ² as a solid content. A modified thermoplastic polymer film characterized by comprising:   The modified thermoplastic polymer film according to claim 9, wherein the surface treatment is a corona discharge treatment, and the wetting tension of the treated surface is 35 mN / m or more.   The modified thermoplastic polymer film according to claim 9 or 10, which is an agricultural coating film. The manufacturing method of the modified thermoplastic polymer film characterized by passing through the following 1st process and the following 2nd process.
1st process: The process which surface-treats to a thermoplastic polymer film, and sets the wet tension of a process surface to 35 mN / m or more 2nd process: With respect to the surface treatment surface of the thermoplastic polymer film obtained at the 1st process The process of apply | coating the composition for thermoplastic polymer film coatings as described in any one of Claims 1-8 so that it may become 0.1-2.0 g / m < ² > as solid content.   The method for producing a modified thermoplastic polymer film according to claim 12, wherein the surface treatment is a corona discharge treatment, and the wet tension of the treated surface is 35 mN / m or more.